EP1371409B1 - Film de separation, element de film de separation, module de film de separation, dispositif de traitement d'eaux usees et residuaires, et procede de fabrication de film de separation - Google Patents

Film de separation, element de film de separation, module de film de separation, dispositif de traitement d'eaux usees et residuaires, et procede de fabrication de film de separation Download PDF

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Publication number
EP1371409B1
EP1371409B1 EP02711312A EP02711312A EP1371409B1 EP 1371409 B1 EP1371409 B1 EP 1371409B1 EP 02711312 A EP02711312 A EP 02711312A EP 02711312 A EP02711312 A EP 02711312A EP 1371409 B1 EP1371409 B1 EP 1371409B1
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EP
European Patent Office
Prior art keywords
separation membrane
porous
porous substrate
resin
resin layer
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EP02711312A
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German (de)
English (en)
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EP1371409A1 (fr
EP1371409A4 (fr
Inventor
Hirofumi Morikawa
Shuji Furuno
Masahiro Henmi
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Toray Industries Inc
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Toray Industries Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/18—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/081—Manufacturing thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/082—Flat membrane modules comprising a stack of flat membranes
    • B01D63/0822—Plate-and-frame devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation
    • B01D67/00165—Composition of the coagulation baths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2315/00—Details relating to the membrane module operation
    • B01D2315/06—Submerged-type; Immersion type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/18—Use of gases
    • B01D2321/185—Aeration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration

Definitions

  • the present invention relates to a separation membrane suitably used in purification of sewage, namely, domestic wasted water exhausted from life environments such as cooking, washing, taking a bath, and relieving nature, and of wastewater discharged from manufacturing plants, restaurants, fish processing factories, and food processing factories.
  • the present invention also relates to a method for making the separation membrane module.
  • the present invention relates to a separation membrane element, a separation membrane module, and a sewage treatment apparatus including the separation membrane.
  • microfiltration membrane Separation membranes have recently been used for purification of sewage and wastewater. Though various types and shapes of separation membrane are known, a flat membrane called a microfiltration membrane attracts attention.
  • the microfiltration membrane is generally formed as follows. A resin solution containing a pore-forming agent is applied onto a surface of a porous substrate such as woven or nonwoven fabric or is impregnated into the porous substrate, and the resin is coagulated to form a porous resin layer on the porous substrate. The porous resin layer functions as a separation layer.
  • the flat membrane does not have a large effective area per unit area, compared with other types of separation membrane, for example, a hollow fiber membrane; hence, the flat membrane is required for achieving high water permeability while maintaining a micropore size corresponding to the object to be filtered.
  • the porosity is increased in order to achieve high water permeability
  • the micropore size excessively increases or surface cracks causing a decrease in rejection occurs.
  • the micropore size is decreased in order to achieve a high rejection, the water permeability inevitably decreases. Accordingly, a high rejection and high water permeability are basically incompatible. It is difficult to achieving balanced compatibility therebetween.
  • separation membranes for sewage water undergo heavy collision of solid materials such as sand and sludge in use and heavy collision of bubbles during an aeration process which is performed to supply oxygen into activated sludge and to prevent clogging.
  • the separation membrane must have sufficiently high strength durable to such severe impacts. Such high strength is primarily borne by the porous substrate.
  • the porous resin layer would be separated from the porous substrate during a filtration process and an aeration process in severe cases.
  • a separation membrane comprises a porous substrate and a porous resin layer on at least one surface of the porous substrate, which porous resin layer comprises a resin, a part of which resin permeates into the porous substrate to form, with the porous substrate, a composite layer; in which separation membrane B ⁇ 0.2 ⁇ A , and C / B ⁇ 0.1 wherein A represents the thickness of the porous substrate, B represents the thickness of the porous resin layer and C represents the thickness of the composite layer; and the porous resin layer has an average pore size in the range of 0.01 to 0.2 ⁇ m and a standard deviation of the pore size of 0.01 ⁇ m or less at the surface.
  • the porous resin layer has macrovoids having short diameters of 0.05xA or more wherein A represents the thickness of the porous substrate, and the rejection of micro particles having an average particle size of 0.9 ⁇ m is at least 90%.
  • the average pore size and the standard deviation are determined based on diameters of all micropores which can be observed in a scope of 9.2 ⁇ m by 10.4 ⁇ m by scanning electron microscopy at a magnification of x10,000.
  • a method for making a separation membrane comprises the steps of applying a resin solution containing a resin, a pore-forming agent, a solvent for the resin and a non-solvent for the resin, onto at least one surface of a porous substrate having a density of 0.7 g/cm 3 or less to form a coating film and to impregnate the porous substrate with the solution; and immersing the porous substrate into a coagulation bath containing a non-solvent for the resin to coagulate the resin and to form a porous resin layer on the surface of the porous substrate, wherein the pore-forming agent comprises polyethylene glycol having a weight average molecular weight of at least 10,000 as a major component.
  • the present invention is directed to a separation membrane element including the separation membrane, a separation membrane module including the separation membrane elements, and a sewage treatment apparatus including the separation membrane module.
  • the separation membrane according to the present invention comprises a porous substrate and a porous resin layer, which functions as a separation layer, on at least one surface of the porous substrate.
  • the porous resin layer comprises a resin and part of the resin permeates into the porous substrate to form a composite layer with the porous substrate.
  • the porous resin layer does not include the composite layer.
  • the porous substrate supports the porous resin layer and imparts strength to the separation membrane.
  • Both organic materials and inorganic materials can be used as the porous substrate, and organic fibers are preferably used since they are lightweight.
  • More preferable porous substrates are woven or nonwoven fabrics of organic fibers such as cellulose fibers, cellulose triacetate fibers, polyester fibers, polypropylene fibers, and polyethylene fibers.
  • nonwoven fabrics are preferable because the control of density is easy and the nonwoven fabrics can be readily produced with reduced costs.
  • a significantly thin porous substrate does not have a sufficient strength for the use in the separation membrane, and a significantly thick porous substrate causes a decrease in water permeability.
  • the thickness of the porous substrate is preferably in the range of 50 ⁇ m to 1 mm, and more preferably 70 ⁇ m to 500 ⁇ m.
  • the porous resin layer functions as a separation layer.
  • materials used for the porous resin layer include polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinylidene fluoride resins, polysulfone resins, polyethersulfone resins, polyimide resins, and polyether imide resins. These resins may contain other resins, as long as these resins are primary components.
  • the "primary components" means that at least 50% and preferably at least 60% of the above resin is contained.
  • polyvinyl chloride resins polyvinylidene fluoride resins
  • polysulfone resins polysulfone resins
  • polyethersulfone resins since films can be readily formed from these resins by a solution process and these resins exhibit high mechanical and chemical resistances.
  • the most preferable resins are polyvinylidene fluoride and mixtures containing polyvinylidene fluoride as the primary component.
  • the thickness of the porous resin layer is preferably in the range of 1 ⁇ m to 500 ⁇ m and more preferably in the range of 5 ⁇ m to 200 ⁇ m.
  • a significantly thin porous resin causes exposition of the porous substrate, resulting in adhesion of contaminants to the porous substrate. In such a case, the filtration pressure will increase and the filtering performance may not be restored sufficiently after washing.
  • a significantly thick porous resin layer may cause a decrease in water permeability.
  • Part of the resin of the porous resin layer permeates into at least the surface layer of the porous substrate to form a composite layer with the porous substrate at least at the surface layer.
  • the resin permeating into the porous substrate is firmly fixed on the porous substrate by the so-called “anchor effect" and is not detached from the porous substrate.
  • the porous resin layer may be formed on one surface of the porous substrate or the porous resin layers may be formed on both surfaces thereof. If the porous resin layer is provided on one surface, the separation membrane with high water permeability can be readily formed. If the porous resin layers are provided on two surfaces, the separation membrane can maintain high performance in use for a long time.
  • the porous resin layers may be symmetrical or asymmetrical to the porous substrate. Also if the porous resin layers are provided on both surfaces, the both porous resin layers may be continuous through the composite layer or may be discontinuous.
  • the separation membrane according to the present invention has an average pore diameter in the range of 0.01 ⁇ m to 0.2 ⁇ m and a standard deviation of pore size of 0.1 ⁇ m or less at the surface of the porous resin layer.
  • the separation membrane satisfying such ranges exhibits both a high permeability for a long time without clogging and a high rejection, which means that fungus and sludge do not leak.
  • a smaller average pore size may cause decreased water permeability.
  • the average pore size is preferably at least 0.02 ⁇ m and more preferably at least 0.04 ⁇ m. If the porous resin layers are provided on two surfaces of the porous substrate, at least one of the porous resin layers must satisfy the above conditions.
  • the average pore size and the standard deviation are determined based on diameters of all micropores which can be observed in a scope of 9.2 ⁇ m by 10.4 ⁇ m by scanning electron microscopy at a magnification of ⁇ 10,000.
  • the separation membrane according to the present invention satisfies the following inequalities: B ⁇ 0.2 ⁇ A , and C / B ⁇ 0.1 wherein A represents the thickness of the porous substrate, B represents the thickness of the porous resin layer, and C represents the thickness of the composite layer. If the thickness of the porous resin layer is smaller than 0.2 ⁇ A, the strength is insufficient to the separation layer. If the ratio C/B is smaller than 0.1, the porous resin layer is readily detached from the porous substrate. On the contrary, if the ratio C/B is extraordinarily large, the water permeability will decrease. Thus, the ratio C/B generally satisfies the following relationship: 0.1 ⁇ C/B ⁇ 100 and preferably 0.2 ⁇ C/B ⁇ 50.
  • the porous resin layer contains macrovoids having specific sizes.
  • the "macrovoids” means pores which are present in the porous resin layer and have larger diameters than the pore diameter at the surface.
  • the macrovoids are useful for maintaining the strength of the porous resin layer while improving the water permeability.
  • the macrovoids have short diameters of at least 0.05 ⁇ A. A smaller short diameter causes a significant decrease in water permeability, though it increases the strength of the porous resin layer. On the other hand, an extraordinarily large short diameter causes decreased strength of the porous resin layer.
  • the upper limit of sizes of the macrovoids is preferably 1xA or less.
  • the thickness of the porous resin layer, the thickness of the composite layer, and the sizes of the macrovoids in the porous resin layer can be determined by observing a cross-section perpendicular to the surface of the porous resin layer with a scanning electron microscope.
  • porous resin layers are provided on two surfaces, the following inequalities are preferably satisfied: 2 d A ⁇ d C 2 d B ⁇ d C wherein d A represents the average pore size at the surface of one of the porous resin layers, d B represents the average pore size at the surface of the other porous resin layer, and d C represents the average pore size in the central cross-section of the separation membrane in the thickness direction.
  • d A represents the average pore size at the surface of one of the porous resin layers
  • d B represents the average pore size at the surface of the other porous resin layer
  • d C represents the average pore size in the central cross-section of the separation membrane in the thickness direction.
  • the rejection of micro particles having an average particle size of 0.9 ⁇ m is preferably at least 90%.
  • a rejection of less than 90% causes leakage of fungus and sludge, clogging due to fungus and sludge, an increased differential filtration pressure, and a significantly decreased life.
  • the rejection is determined as follows.
  • the stock dispersion Using a stock dispersion containing purified water through a reverse osmosis membrane and 10 ppm of polystyrene latex microparticles having an average diameter of 0.9 ⁇ m (nominal diameter: 0.940 ⁇ m, the standard deviation: 0.0796 ⁇ m), the stock dispersion is allowed to permeate through the separation membrane at a head height of 1 m while the stock dispersion is stirred.
  • the separation membrane according to the present invention may be combined with a support to prepare a separation membrane element.
  • the separation membrane according to the present invention is arranged on at least one surface of a supporting plate as the support.
  • This separation membrane element can be preferably used in sewage treatments as described below.
  • the separation membranes are preferably arranged on both surfaces of the supporting plate to increase water permeability.
  • the configuration of the separation membrane element is not limited. Preferable configurations of the separation membrane element will now be described with reference to the drawings.
  • the element has a rigid supporting plate 1, and channel members 2 and separation membranes 3 arranged on both surfaces of the supporting plate 1 in that order.
  • the supporting plate 1 has projections 4 and recesses 5.
  • the contaminants in the liquid are removed by the separation membrane 3.
  • the channel members 2 are provided so that water permeating through the separation membrane 3 effectively flows toward the supporting plate 1.
  • the filtered water reaching the supporting plate 1 flows in the recesses of the supporting plate 1 toward the exterior.
  • any supporting plate 1 may be used in the present invention as long as a plurality of projections and recesses are provided both surfaces of a plate.
  • the recesses constitute a plurality of grooves arranged in parallel at a constant pitch so that the distance to the outlet for the filtered water and the channel resistance become uniform. In such a configuration, the filtered water uniformly flows on the membrane.
  • the width of the recesses is preferably in the range of 1 mm to 20 mm and more preferably 1.5 mm to 5 mm to maintain high water permeability and to prevent sinking of the channel members 2 and the separation membranes 3 under severe aeration conditions.
  • the depth of the recesses 5 is determined within the range of 1 mm to 10 mm to suppress the thickness of the element and to secure channels for the filtered water.
  • the void fraction formed by the recesses of the supporting plate is preferably in the range of 15% to 85% to keep the strength of the supporting plate and to suppress the flow resistance of the filtered water.
  • the void fraction means the volume fraction of voids formed by the recesses to a void fraction of a hollow rectangular parallelepiped of 100%. At a void fraction of less than 15%, the flow resistance is too high to effectively collect the filtered water. At a void fraction exceeding 85%, the strength of the supporting plate significantly decreases.
  • the supporting plate 1 is preferably composed of a rigid material having a tensile strength of about 15 MPa according to ASTM testing method D638.
  • preferable materials are metals such as stainless steel; resins such as acrylonitrile-butadiene-styrene copolymers (ABS resins), polyethylene, polypropylene, and vinyl chloride; and composite materials such as fiber-reinforced plastics (RFP).
  • the channel member 2 preferably has a thickness in the range of 0.1 mm to 5 mm to decrease the thickness of the element while maintaining the flow channels. It is preferable that a material having a high porosity such as a plastic net be used to reduce pressure drop.
  • the porosity of the channel member is preferably in the range of 40% to 96%.
  • the separation membrane element according to the present invention is preferably provided with a frame 6 at the periphery of the supporting plate 1.
  • the separation membrane 3 may be disposed between the supporting plate 1 and the frame 6 or may be fixed onto the outer surface of the frame 6.
  • the fixing process may be a bonding process using a resin, a welding process of the separation membrane itself, and any other bonding process.
  • the frame 6, which is formed by injection molding or extrusion, may be engaged on the periphery of the supporting plate 1, which is formed by economical extrusion, to suppress fabrication costs.
  • the frame 6 preferably has a U-shaped cross-section so that the supporting plate 1 can be readily engaged.
  • the water permeating through the separation membrane 3 flows in the channel member 2 and the recesses 5 of the supporting plate 1 toward the exterior of the element through a filtered water outlet 7.
  • the separation membrane according to the present invention can be preferably used in sewage treatment apparatuses.
  • the method for using the separation membrane is not limited. A preferable method for use will be described below.
  • a plurality of the elements 9 are accommodated in parallel to each other in the housing so as to form a space between the surfaces of the separation membranes 3 (Fig. 7), in order to form the separation membrane module 10.
  • This separation membrane module 10 as shown in Fig. 12, is used by immersing into water to be treated such as organic wastewater stored in a reservoir 11.
  • the separation membrane module 10 has a plurality of the elements 9 which are vertically arranged and an air diffuser 12 for supplying air from a blower 13 to the surfaces of the separation membranes therein, and has a pump 14, which sucks in filtered water, downstream of the separation membrane module 10.
  • water to be treated such as wastewater
  • water permeating through the separation membranes 3 by the suction force of the pump 14 and suspended solids such as microorganism particles and inorganic particles which do not permeate.
  • the water permeating through the separation membranes 3 flows through a flow pathway formed of the channel member 2, the recesses 5 of a supporting plate 1, a collecting conduit 8 formed in the frame 6, and the filtered water outlet 7 toward the exterior of the reservoir 11.
  • the air diffuser 12 generates bubbles, which generate an upward flow parallel to the surfaces of the membranes of the elements 9 by the airlift effect. The upward flow removes the filtration residue deposited on the surfaces of the membranes.
  • Another preferable embodiment of the separation membrane element according to the present invention has a container and a spirally wound separation membrane according to the present invention accommodated in the container.
  • the element in this embodiment will now be described with reference to Fig. 13.
  • a separation membrane element 15 includes folded separation membranes 18, each containing a mesh spacer 19. These separation membranes 18 are spirally wounded around a central pipe 16 together with channel members 17.
  • a brine seal 20 is provided at one end of the winding structure. In each element 15, supply water having a given pressure from the brine seal 20 flows through the mesh spacer 19 and permeates through the separation membrane 18. The filtered water is collected through the central pipe 16.
  • This element has a larger membrane area and thus has high water permeability compared with the above-described elements including the supporting plate. Since this element, however, exhibit relatively low supply effectively due to retention of contaminants at the supply side; this is suitable for treatment of seawater, brine, and river water.
  • the activated-sludge effluent is preliminarily treated by flocculation and precipitation, sand filtration, micro filtration membrane, or ultra filtration membrane.
  • the preliminary treatments may be employed alone or in combination.
  • the separation membrane according to the present invention may be produced by the following method.
  • a coating film is formed on a surface or surfaces of the above-described porous substrate with a resin solution containing the above-described resin, a pore-forming agent, and a solvent, and the porous substrate is impregnated with the solvent. Then, the porous substrate is immersed into a coagulation bath containing a non-solvent to coagulate the resin and to form a porous resin layers on the surfaces of the porous substrate.
  • the solution contains a non-solvent.
  • the temperature of the solution is preferably selected from the range of 15°C to 120°C in view of film formability.
  • the density of the porous substrate is preferably 0.7 g/cm 3 or less and more preferably 0.6 g/cm 3 or less.
  • the porous substrate can hold the resin forming the porous resin layer, so that an adequate composite layer or composite layers of the porous substrate and the resin is formed. Since a significantly low density causes a decreased in strength of the separation membrane, the density is preferably at least 0.3 g/cm 3 .
  • the density represents an apparent density, which can be determined from the area, the thickness, and the weight of the porous substrate.
  • the pore-forming agent is extracted from the resin layer to form pores in the resin layer when the porous substrate is immersed in the coagulation bath.
  • the pore-forming agent has high solubility in the coagulation bath.
  • the pore-forming agents are inorganic salts such as calcium chloride and calcium carbonate.
  • the pore-forming agents may be polyoxyalkylenes, e.g., polyethylene glycol and polypropylene glycol; and water-soluble polymers, e.g., polyvinyl alcohol, polyvinyl butyral, and polyacrylic acids; and glycerin.
  • the pore-forming agent may be appropriately selected according to the resin.
  • a polymer primarily containing polyethylene glycol is preferable. More preferably, a polymer primarily containing polyethylene glycol having a weight average molecular weight of at least 10,000 is used in view of balance among the surface pore size, pore size distribution, and permeability.
  • the solvent dissolves the resin.
  • the solvent acts on the resin and the pore-forming agent and promotes the formation of the porous resin layer.
  • solvents include N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, and methyl ethyl ketone.
  • NMP N-methylpyrrolidone
  • DMAc N,N-dimethylacetamide
  • DMF N,N-dimethylformamide
  • DMSO dimethyl sulfoxide
  • acetone methyl ethyl ketone
  • the non-solvent does not dissolve the resin.
  • the non-solvent controls the coagulation rate of the resin and thus the size of the micropores and macrovoids.
  • the non-solvents are water and alcohols such as methanol and ethanol. Among these, water and methanol are preferable in view of easy sewage treatment and economical advantages.
  • the non-solvent may be a mixture thereof.
  • the resin solution preferably contains 5 to 30 weight percent of resin, 0.1 to 15 weight percent of pore-forming agent, 40 to 94.9 weight percent of solvent, and 0 to 20 weight percent of non-solvent.
  • a significantly low resin content may cause a decrease in strength of the porous resin layer, whereas a significantly high resin content may cause a decrease in water permeability.
  • a significantly low pore-forming agent content may cause a decrease in water permeability, whereas a significantly high pore-forming agent content may cause a decrease in strength of the porous resin layer.
  • the pore-forming agent content is extremely high, the pore-forming agent remains in the porous resin layer and may dissolve in use, resulting in aggravation of water quality and fluctuation or water permeability.
  • the pore-forming agent content in the solution is more preferably in the range of 0.5 to 10 weight percent. At a significantly small volume of solvent, the solution is readily gelated, whereas ata significantly large volume of solvent, the strength of the porous resin layer may decrease .
  • the solvent content in the solution is more preferably in the range of 60 to 90 weight percent.
  • the solution contains a non-solvent because the size of the micropores on the surface of the porous resin layer becomes uniform. Also, the size of the macrovoids is readily controlled. A significantly large non-solvent content, however, causes ready gelation of the solution.
  • the solvent content in the solution is in the range of 40 to 94.8 weight percent while the non-solvent content is in the range of 0.1 to 20 weight percent. More preferably, the solvent content is in the range of 40 to 94.4 weight percent while the non-solvent content is in the range of 0.5 to 15 weight percent.
  • the coagulation bath may contain a non-solvent or a mixture of a non-solvent and a solvent.
  • the non-solvent content in the coagulation bath is preferably at least 80 weight percent.
  • a significantly small non-solvent content causes a delay of coagulation of the resin, resulting in an increase in micropore size and inhibiting the formation of the macrovoids. More preferably, the non-solvent content is in the range of 85 to 100 weight percent.
  • the non-solvent content in the coagulation bath is preferably lower than that when the solution contains the non-solvent. That is, the non-solvent content is preferably at least 60 weight percent.
  • a large non-solvent content delays coagulation of the resin, resulting in the formation of the porous resin layer having a dense surface and containing internal macrovoids; however, a large non-solvent content may form fine cracks on the surface of the porous resin layer.
  • the non-solvent content is more preferably in the range of 60 to 99 weight percent.
  • the solvent content in the coagulation bath is adjusted to control the pore size on the surface of the porous resin layer and the size of the macrovoids.
  • a significantly high bath temperature excessively promotes coagulation whereas a significantly low bath temperature excessively delays coagulation.
  • the bath temperature is preferably in the range of 15°C to 80°C and more preferably 20°C to 60°C.
  • a coating film from the solution on the porous substrate may be formed by applying the solution onto the porous substrate or immersing the porous substrate into the solution.
  • the solution may be applied onto one surface or two surfaces of the porous substrate.
  • the density of the porous substrate is preferably 0.7 g/cm 3 or less to achieve adequate impregnation of the porous substrate with the solution, though the preferable density depends on the composition of the solution.
  • PVDF polyvinylidene fluoride
  • PEG polyethylene glycol
  • DMAc N, N-dimethylacetamide
  • the cross-section perpendicular to the surface of the separation membrane was observed with the scanning electron microscope.
  • Macrovoids having a short diameter of about 30 ⁇ m (about 0.14 ⁇ A > 0.05 ⁇ A) were distributed in the porous resin layer and the composite layer.
  • the thickness (B) of the porous resin layer was about 110 ⁇ m and the thickness (C) of the composite layer was about 220 ⁇ m, which was substantially equal to the thickness of the porous substrate.
  • B was equal to about 0.5 ⁇ A, which was larger than 0.2 ⁇ A
  • C/B was equal to about 2, which was larger than 0.1.
  • the rejection for fine particles having an average diameter of 0.9 ⁇ m was measured.
  • the rejection was 98%.
  • the volume of permeating water was measured with a reverse osmosis membrane at a head height of 1 m using purified water at 25°C.
  • the volume of the permeating water was 37 ⁇ 10 -9 m 3 /m 2 ⁇ s ⁇ Pa.
  • the resulting separation membranes 3 were bonded onto plastic nets which were provided on both surfaces of a frame having a filtered water outlet 7 at the top and having a length of 320 mm, a width of 220 mm, and a length of 5 mm to form an element.
  • a module shown in Fig. 11 was fabricated. The module was placed into a reservoir having an air nozzle 12 at the bottom and having a depth of 500 mm, a width of 150 mm, and a height of 700 mm as shown in Fig. 12.
  • Activated sludge having a concentration of 3,000 mg/liter was placed in the reservoir and air was supplied from the air nozzle at a rate of 20 liter/min, while permeation test was performed at a linear permeation rate of 0.4 m/day.
  • a differential filtration pressure, which was converted to 25°C, was small, i.e., 0.5 kPa at an initial stage and 0.8 kPa at 1,000 hours later. No damage or detachment of the porous resin layer was observed after 1,000 hours.
  • a separation membrane shown in Figs. 3 and 4 was prepared as in EXAMPLE 1, but the solution used had the following composition.
  • the porous resin layer and the composite layer of the resulting separation membrane were observed in the scope of 9.2 ⁇ m by 10.4 ⁇ m by scanning electron microscopy at a magnification of ⁇ 10,000.
  • the average of sizes of all observable micropores was 0.15 ⁇ m and the standard deviation thereof was 0.12 ⁇ m.
  • Microcracks with a width of 1 to 2 ⁇ m occurred at some places.
  • the cross-section perpendicular to the surface of the separation membrane was observed with the scanning electron microscope.
  • Macrovoids having a short diameter of about 30 ⁇ m (about 0.14 ⁇ A > 0.05 ⁇ A) were distributed in the porous resin layer and the composite layer.
  • the thickness (C) of the composite layer was about 220 ⁇ m, which was substantially equal to the thickness of the porous substrate.
  • the measured rejection of the separation membrane for fine particles having an average diameter of 0.9 ⁇ m was 60%.
  • the volume of permeating water measured as in EXAMPLE 1 was 39 ⁇ 10 -9 m 3 /m 2 ⁇ s ⁇ Pa.
  • a permeation test was performed as in EXAMPLE 1.
  • a differential filtration pressure which was converted to 25°C, was 0.5 kPa at an initial stage and was increased to 6 kPa at 1,000 hours later. No detachment of the porous resin layer was observed after 1,000 hours.
  • a separation membrane shown in Figs. 5 and 6 was prepared as in EXAMPLE 1, but a polyester nonwoven fabric having a density of 0.90 g/cm 3 and a thickness (A) of 101 ⁇ m was used as the porous substrate.
  • the porous resin layer and the composite layer of the resulting separation membrane were observed in the scope of 9.2 ⁇ m by 10.4 ⁇ m by scanning electron microscopy at a magnification of ⁇ 10,000.
  • the average of sizes of all observable micropores was 0.067 ⁇ m and the standard deviation thereof was 0.033 ⁇ m.
  • the cross-section perpendicular to the surface of the separation membrane was observed with the scanning electron microscope. No macrovoids were observed.
  • the thickness (3) of the porous resin layer was about 30 ⁇ m, but no composite layer (C) was observed.
  • B was about 0.14 ⁇ A, which is less than 0.2 ⁇ A
  • C/B was 0, which is less than 0.1.
  • the measured rejection of this separation membrane for fine particles having an average diameter of 0.9 ⁇ m was 98%.
  • the volume of permeating water measured as in EXAMPLE 1 was 10 ⁇ 10 -9 m 3 /m 2 ⁇ s ⁇ Pa.
  • a permeation test was performed as in EXAMPLE 1.
  • a differential filtration pressure, which was converted to 25°C, was 0.8 kPa at an initial stage. After 96 hours, the porous resin layer was detached from the porous substrate.
  • a separation membrane was prepared as in EXAMPLE 1, but the polyester nonwoven fabric after applying the solution was immersed in an aqueous 60-weight% DMAc solution for 5 minutes.
  • the surface, away from the porous substrate, of the porous resin layer of the resulting separation membrane was observed in the scope of 9.2 ⁇ m by 10.4 ⁇ m by scanning electron microscopy at a magnification of ⁇ 10,000.
  • the average of sizes of all observable micropores was 0.4 ⁇ m and the standard deviation thereof was 0.1 ⁇ m.
  • the measured rejection of this separation membrane for fine particles having an average diameter of 0.9 ⁇ m was 80%.
  • the volume of permeating water measured as in EXAMPLE 1 was 40 ⁇ 10 -9 m 3 /m 2 ⁇ s ⁇ Pa.
  • the solution prepared in EXAMPLE 1 was cooled to 25°C and was applied onto two surfaces of the polyester nonwoven fabric as in EXAMPLE 1. Immediately after, the polyester nonwoven fabric was immersed in pure water at 25°C for 5 minutes, and was immersed in hot water at 80°C three times to remove DMAc and PEG. A separation membrane was prepared in such a manner.
  • the cross-section perpendicular to the surface of the separation membrane was observed with a scanning electron microscope.
  • the thickness (A) of the porous substrate was 220 ⁇ m, and the distances from the center of the porous substrate to the two surfaces of the porous resin layers were 150 ⁇ m and 130 ⁇ m.
  • the thicker porous resin layer had a thickness of 40 ⁇ m and the thinner porous resin layer had a thickness of 20 ⁇ m, resulting in a total thickness (B) of 60 ⁇ m.
  • the composite layer had a thickness (C) of about 220 ⁇ m, which was equal to the thickness of the porous substrate.
  • B was about 0.27 ⁇ A, which is larger than 0.2 ⁇ A
  • C/B was about 3.7, which is larger than 0.1.
  • the average pore diameter (d C ) in the center of the cross-section of the porous resin layer was 0.4 ⁇ m and the standard deviation thereof was 0.1 ⁇ m.
  • the average pore diameter (d A ) in the surface, away from the porous resin layer, of the porous substrate was 0.07 ⁇ m and the standard deviation thereof was 0.03 ⁇ m
  • the average pore diameter (d B ) in the surface, near the porous resin layer, of the porous substrate was 0.07 ⁇ m and the standard deviation thereof was 0.03 ⁇ m.
  • the average pore diameter and the standard deviation thereof were determined based on all micropores which can be observed within a scope of 9.2 ⁇ m by 10.4 ⁇ m by scanning electron microscopy at a magnification of ⁇ 10,000.
  • 2d A 0.14, which is smaller than d C
  • 2d B 0.14, which is smaller than d C .
  • the measured rejection of this separation membrane for fine particles having an average diameter of 0.9 ⁇ m was 99%.
  • the volume of permeating water measured as in EXAMPLE 1 was 30 ⁇ 10 -9 m 3 /m 2 ⁇ s ⁇ Pa.
  • a permeation test was performed as in EXAMPLE 1.
  • a differential filtration pressure, which was converted to 25°C, was 0.6 kPa at an initial stage and was 1.0 kPa at 1,000 hours later. No detachment of the porous resin layer was observed after 1,000 hours.
  • the solution prepared as in EXAMPLE 1 was cooled to 25°C and was applied onto two surfaces of the same polyester nonwoven fabric as in EXAMPLE 1. Immediately after, the polyester nonwoven fabric was immersed in an aqueous 60-weight % DMAc solution at 25°C for 5 minutes, and was immersed in hot water at 80°C three times to remove DMAc and PEG. A separation membrane was prepared in such a manner.
  • the cross-section perpendicular to the surface of the separation membrane was observed with a scanning electron microscope.
  • the thickness (A) of the porous substrate was 220 ⁇ m, and the distances from the center of the porous substrate to the two surfaces of the porous resin layers were 150 ⁇ m and 130 ⁇ m.
  • the thicker porous resin layer had a thickness of 40 ⁇ m and the thinner porous resin layer had a thickness of 20 ⁇ m, resulting in a total thickness (B) of 60 ⁇ m.
  • the composite layer had a thickness (C) of about 220 ⁇ m, which was equal to the thickness of the porous substrate.
  • B was about 0.27 ⁇ A, which is larger
  • a permeation test was performed as in EXAMPLE 1.
  • a differential filtration pressure, which was converted to 25°C, was 0.6 kPa at an initial stage and was 1.0 kPa at 1,000 hours later. No detachment of the porous resin layer was observed after 1,000 hours.
  • the solvent prepared as in EXAMPLE 1 was cooled to 25°C and was applied onto two surfaces of the same polyester nonwoven fabric as in EXAMPLE 1. Immediately after, the polyester nonwoven fabric was immersed in an aqueous 60-weight% DMAc solution at 25°C for 5 minutes, and was immersed in hot water at 80°C three times to remove DMAc and PEG. A separation membrane was prepared in such a manner.
  • the cross-section perpendicular to the surface of the separation membrane was observed with a scanning electron microscope.
  • the thickness (A) of the porous substrate was 220 ⁇ m, and the distances from the center of the porous substrate to the two surfaces of the porous resin layers were 150 ⁇ m and 130 ⁇ m.
  • the thicker porous resin layer had a thickness of 40 ⁇ m and the thinner porous resin layer had a thickness of 20 ⁇ m, resulting in a total thickness (B) of 60 ⁇ m.
  • the composite layer had a thickness (C) of about 220 ⁇ m, which was equal to the thickness of the porous substrate.
  • B was about 0.27 ⁇ A, which is larger than 0.2xA
  • C/B was about 3.7, which is larger than 0.1.
  • the average pore diameter (d C ) in the center of the cross-section of the porous resin layer was 0.6 ⁇ m.
  • the average pore diameter (d A ) in the surface, away from the porous resin layer, of the porous substrate was 0.4 ⁇ m, whereas the average pore diameter (d B ) in the surface, near the porous resin layer, of the porous substrate was 0.4 ⁇ m.
  • the average pore diameter was determined based on all micropores which can be observed within a scope of 9.2 ⁇ m by 10.4 ⁇ m by scanning electron microscopy at a magnification of ⁇ 10,000.
  • 2d A 0.08, which is larger than d C
  • 2d B 0.8, which is larger than d C .
  • the measured rejection of this separation membrane for fine particles having an average diameter of 0.9 ⁇ m was 80%.
  • the volume of permeating water measured as in EXAMPLE 1 was 40 ⁇ 10 -9 m 3 /m 2 ⁇ s ⁇ Pa.
  • the separation membrane according to the present invention has a high rejection and high permeability and does not clog. Furthermore, the separation membrane can be readily produced by a method for making a separation membrane according to the present invention.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)

Claims (23)

  1. Une membrane de séparation comprenant un substrat poreux et une couche de résine poreuse sur au moins une surface du substrat poreux, couche de résine poreuse qui comprend une résine, résine dont une partie passe à travers le substrat poreux pour former, avec le substrat poreux, une couche composite ;
    membrane de séparation dans laquelle B ≥ 0 , 2 × A ,
    Figure imgb0011
     et C / B ≥ 0 , 1
    Figure imgb0012
    où A représente l'épaisseur du substrat poreux, B représente l'épaisseur de la couche de résine poreuse et C représente l'épaisseur de la couche composite ; et
    la couche de résine poreuse a une dimension moyenne des pores dans la gamme de 0,01 à 0,2 µm et un écart standard de la dimension des pores de 0,1 µm ou moins au niveau de la surface.
  2. Une membrane de séparation selon la revendication 1, dans laquelle le substrat poreux a une masse volumique de 0,7 g/cm3 ou moins.
  3. Une membrane de séparation selon la revendication 1 ou la revendication 2, dans laquelle le substrat poreux comprend des fibres organiques.
  4. Une membrane de séparation selon l'une quelconque des revendications précédentes, dans laquelle le substrat poreux comprend une étoffe non lissée
  5. Une membrane de séparation selon l'une quelconque des revendications précédentes, dans laquelle la résine comprend du fluorure de polyv inylidene en tant q u'élément constitutif principal.
  6. Une membrane de séparation selon l'une quelconque des revendications précédentes, dans laquelle la couche de résine poreuse comprend des macro-vides ayant de court s diamètres, mesurés dans une section transversale perpendiculaire à la surface de la couche de résine poreuse, de 0,05 xA ou davantage, et dans laquelle la réjection par la membrane de séparation des micro particules ayant une granulométrie moyenne de 0,9 µm est d'au moins 90%.
  7. Une membrane de séparation selon l'une quelconque des revendications précédentes, dans laquelle le substrat poreux comprend les couches de résine poreuses sur deux surfaces, et 2 d A ≤ d C
    Figure imgb0013
     2 d B ≤ d C
    Figure imgb0014
    où dA représente la dimension moyenne des pores au niveau de la surface d'une des couches de résine poreuse, dB représente la dimension moyenne des pores au niveau de la surface de l'autre couche de résine poreuse, et dC représente la dimension moyenne des pores dans la section transversale centrale de la membrane de séparation dans la direction de l'épaisseur.
  8. Utilisation, dans un appareil de traitement d'eau x usées, d'une membrane de séparation selon l'une quelconque des revendications précédentes.
  9. Un élément de membrane de séparation comprenant une membrane de séparation selon l'une quelconque des revendications 1 à 7 et un support.
  10. Un élément de membrane de séparation selon la revendication 9 comprenant, en tant que support, une plaque de support et une membrane de séparation selon l'une quelconque des revendications 1 à 7 sur au moins une face de la plaque de support.
  11. Utilisation d'un élément de membrane de séparation selon la revendication 9 ou la revendication 10 dans u ne séparation d'eaux usées.
  12. Un module de membrane de séparation comprenant une pluralité d'éléments de membrane de séparation et un boîtier contenant les éléments de membrane de séparation, chaque élément de membrane de séparation comprenant une membrane de séparation, où les membranes de séparation comprennent des membranes selon l'une quelconque des revendications 1 à 7.
  13. Un module de membrane de séparation selon la revendication 12, dans lequel les éléments de membrane de séparation sont disposés de manière sensiblement parallèle l'un à l'autre de manière à former des espaces entre les membranes de séparation voisines.
  14. Utilisation, dans un traitement d'eau x usées, d'un module de membrane de séparation selon la revendication 12 ou la revendication 13, dans laquelle le module de membrane de séparation est plongé dans les eaux usées à traiter.
  15. Un appareil de traitement d'eau x usées comprenant un module de membrane de séparation selon la revendication 12 ou la revendication 13.
  16. Un procédé de réalisation d'une membrane de séparation comprenant les étapes consistant à :
    appliquer une solution de résine contenant une résine, un agent de formation de pores qui comprend du polyéthylène glycol ayant un poids moléculaire moyen en poids d'au moins 10 000 en tant qu'élément constitutif principal, un solvant pour la résine et un non-solvant pour la résine, sur au moins une surface d'un substrat poreux ayant une masse volumique de 0,7 g/cm 3 ou moins pour former un film de revêtement et pour imprégner le substrat poreux avec la solution ; et
    plonger le substrat poreux dans un bain de coagulation contenant un non-solvant pour la résine afin de coaguler la résine et former une couche de résine poreuse sur la surface du substrat poreux.
  17. Un procédé selon la revendication 16, dans lequel le non-solvant pour la résine est choisi parmi l'eau et 1 es alcools.
  18. Un procédé selon la revendication 17, dans lequel la solution comprend 5 à 30 pour cent en poids de la résine, 0,1 à 15 pour cent en poids de l'agent de formation de pores, 40 à 94,8 pour cent en poids du solvant pour la résine, et 0,1 à 20 pour cent en poids du non-solvant pour la résine.
  19. Un procédé selon la revendication 18, dans lequel le bain de coagulation contient au moins 80 pour cent en poids du non-solvant pour la résine.
  20. Un procédé selon l'une quelconque d es revendications 16 à 19, dans lequel les films de revêtement de la solution sont formés sur deux surface du substrat poreux.
  21. Un procédé selon l'une quelconque des revendications 16 à 20, dans lequel la température de la solution est dans la gamme de 15°C à 120, la température du bain de coagulation étant dans la gamme de 15°C à 80°C.
  22. Un procédé selon l'une quelconque des revendications 16 à 21, dans lequel le substrat poreux comprend une étoffe non tissée.
  23. Un procédé selon l'une quelconque des revendications 16 à 22, dans lequel la résine comprend du fluorure de polyvinylidène en tant qu'élément constitutif principal.
EP02711312A 2001-02-16 2002-02-05 Film de separation, element de film de separation, module de film de separation, dispositif de traitement d'eaux usees et residuaires, et procede de fabrication de film de separation Expired - Lifetime EP1371409B1 (fr)

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JP5310658B2 (ja) 2013-10-09
US20080067127A1 (en) 2008-03-20
CA2432046A1 (fr) 2002-08-22
JPWO2002064240A1 (ja) 2004-06-10
KR20030001426A (ko) 2003-01-06
KR100909528B1 (ko) 2009-07-27
CA2432046C (fr) 2011-04-05
TW514551B (en) 2002-12-21
AU2002230143B2 (en) 2006-06-15
EP1371409A1 (fr) 2003-12-17
CN1457268A (zh) 2003-11-19
DE60208994T2 (de) 2006-08-31
US9649602B2 (en) 2017-05-16
JP5127107B2 (ja) 2013-01-23
US20030150808A1 (en) 2003-08-14
ATE316819T1 (de) 2006-02-15
WO2002064240A1 (fr) 2002-08-22
CN1236842C (zh) 2006-01-18
JP2010221218A (ja) 2010-10-07
DE60208994D1 (de) 2006-04-13
KR100874079B1 (ko) 2008-12-12
EP1371409A4 (fr) 2004-05-12

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